Microbicide compositions

ABSTRACT

The present invention provides a bactericide composition comprising hypochlorous acid or a salt thereof. In particular, the present invention provides a liquid bactericide composition comprising an aqueous solution comprising hypochlorous acid and/or a salt thereof, a surfactant (B) and a pH adjusting agent (C), and having a ph valve in the range of 3 to 8 at 25° C.

This application is the national phase under 35 U.S.C. §371 of PCTInternational Application No. PCT/JP00/08716 which has an Internationalfiling date of Dec. 8, 2000, which designated the United State ofAmerica.

TECHNICAL FIELD

The present invention relates to a bactericide composition comprisinghypochlorous acid or a salt thereof.

PRIOR ART

Conventionally, chlorine-based germicides such as sodium hypochlorite,calcium hypochlorite and sodium dichloroisocyanurate have been generallyused in various environments as germicides and disinfectants. Amongthem, hypochlorites such as sodium hypochlorite are widely used, sincethese are advantageous in costs and effects, and there have been manyproposals so as to further improve the effects thereof with respect togermicidal action and sterilizing action to microbes that are requestedin various fields such as medical and food industries.

For example, JP-A No. 57-61099 has disclosed a liquid germicidalbleaching agent that comprises a hypochlorite, an alkali substance and aspecific cationic surfactant of a quaternary ammonium salt type inrespectively specific weight ratios.

JP-A No. 7-233396 has disclosed a germicidal washing agent for use inmedical equipment such as artificial dialysis devices, which comprises asalt of hypochlorous acid, an alkaline substance and a cationicsurfactant of a quaternary ammonium salt at specified weight ratios.

However, although conventional hypochlorite germicides are effective togeneral bacteria and mold (mycelia) to a certain degree, these fail toprovide sufficient effects to virus having higher resistance tomedicine, spores formed by rod-shaped bacteria and mold spores in thecase of an easy operation.

Moreover, JP-A No. 11-148098 has disclosed a solid-state germicidaldetergent containing an alkaline earth metal of hypochlorous acid likehigh test hypochlorite (calcium hypochlorite). This, however, has notdisclosed anything about germicidal processes in a higher degree, and analkaline earth metal such as calcium causes scales and scum, resultingin degradation in the germicidal effects.

Furthermore, JP-A No. 7-328638 has disclosed a method in which an agentfor reducing surface tension is added to electrolytic acidic water so asto increase the adhering property to the outer surface of agermicide-subject substance; however, although this method is superiorin the germicidal effects, it generates chlorine gas, causing a problemwith safety.

Here, JP-A No. 59-93799 has disclosed a method in which amine oxide isblended in a liquid washing agent comprising a hypochlorite and analkali substance.

Further, JP-A No. 59-98200 has disclosed a method in which amine oxideis used as a thickener for a bleaching agent comprising a salt ofhypochlorous acid; however, these have not described anything aboutgermicidal effects, that is, in particular, germicidal effects to sporesand viruses having high resistance.

DISCLOSURE OF INVENTION

The object of the present invention is to obtain a bactericidecomposition capable of affording a high bactericidal effect while beingexcellent in safety and workability.

The present invention provides a liquid bactericide compositioncomprising an aqueous solution with pH (25° C.) of 3 to 8 comprisinghypochlorous acid and/or a salt thereof (A), a surfactant (B) and a PHadjusting agent (C).

The present invention also provides a bactericide comprising a product(I) comprising hypochlorous acid and/or a salt thereof (A), a product(II) comprising a surfactant (B) and a product (III) comprising a pHadjusting agent (C), wherein the bactericide is prepared as an aqueoussolution comprising (A) and (B) in a weight ratio (A)/(B) of 50/1 to1/50 in use.

This means that the components (A), (B) and (C) can be used together asan aqueous solution at the time of its use. The aqueous solutionpreferably has a pH value of 3 to 8 at 25° C. or 20° C. Since thecomponents (A) and (B) are separately preserved and transported untiljust before use, the bactericide has the excellent stability.

In other words, the present invention provides a method for using abactericide in which the product (I) comprising hypochlorous acid and/ora salt thereof (A), the product (II) comprising a surfactant (B), andthe product (III) comprising a pH adjusting agent (C) are prepared intoan aqueous solution comprising (A), (B) and (C) so that the weight ratioof (A)/(B) is in the range of 50/1 to 1/50 just before use.

In this embodiment of use, the components (A), (B) and (C) may becombined as a kit. Alternatively the components(A), (B) and (C) may be,independently of each other, formulated into their respective individualproducts.

The present invention provides use and a sterilization method of thecomposition, the aqueous solution and the product kit. The methodincludes applying effective doses of them to a desired site or locationfor sterilization.

The preferable surfactant (B) comprises at least one of the surfactantsselected from amphoteric surfactants, cationic surfactants and nonionicsurfactants. Polyoxyalkylene alkylether and polyoxyalkylene phenyl etherare excluded from the preferable nonionic surfactants. Particularlypreferable surfactants are at least one of the surfactants selected fromthe amphoteric surfactants, cationic surfactants and nonionicsurfactant, such as a polyhydric alcohol derivative surfactant. Apreferable amphoteric surfactant is an amine oxide.

A pH adjusting agent (C) is preferably an organic acid or a saltthereof, in particular a saturated dibasic acid or a salt thereof.

The ratio (A)/(B) is preferably in the range of 50/1 to 1/50, or 10/1 to1/10.

The ratio (C)/(A) is preferably in the range of 5/1 to 1/10.

The component (C) may comprise the component (B) before use. In otherwords, the bactericide according to the present invention comprises aproduct (IV) comprising hypochlorous acid and/or a salt thereof (A), anda product (V) comprising the surfactant (B) and the pH adjusting agent(C), and is used as an aqueous solution comprising (A) and (B) in aweight ratio (A)/(B) in the range of 50/1 to 1/50.

The bactericide according to the present invention also comprises aproduct (VI) comprising hypochlorous acid and/or a salt thereof (A) anda surfactant (B), and a product (VII) comprising a pH adjusting agent(C), and is used as an aqueous solution comprising (A) and (B) in aweight ratio (A)/(B) in the range of 50/1 to 1/50.

The bactericide according to the present invention has an antimicrobialeffect on viruses and spores formed by bacillus and fungi that are moreresistant to chemicals. The bactericide is particularly useful incleaning, disinfecting and deodorizing. The composition according to thepresent invention may also comprise a rust preventing agent.

The preferable weight ratio (C) (A) in the aqueous solution is in therange of 2/1 to 1/5, particularly in the range of 1/1 to 1/5.

The preferable weight ratio (A) (B) in the aqueous solution is in therange of 10/1 to 1/10, more preferably in the range of 5/1 to 1/5, andparticularly in the range of 5/1 to 1/2 or 2/1 to 1/2. A range of 20/1to 1/20 is also preferable. More preferably, the range is 20/1 to 1/5,and particularly 20/1 to 1/2. The content of (A) is denoted by a weightratio based on the amount of available chlorine.

The aqueous solution preferably has a pH range of 3 to 8, morepreferably 5 to 8, further preferably 5 to 7, particularly from 5 ormore to less than 7, and more particularly from 6 or more and less than7. The pH value of the solution may be adjusted by the pH adjustingagent that can be selected from an acid, an alkali and a bufferingagent. The component (C) may have functions other than a function foradjusting the pH value. The component having such functions include ahydroxide of an alkali metal, a hydroxide of an alkaline earth metal, aninorganic acid or a salt thereof, and an organic acid or a salt thereof.Hydroxides of alkali metals and alkaline earth metals, and organic acidsor salts thereof are preferable among them.

The component (C) is used in an amount for adjusting the pH value withinthe ranges as described above. A pH range of 3 to 8, preferably 5 to 8,more preferably 5 to 7, further preferably 5 or more to less than 7, andparticularly 6 or more to less than 7 is recommended especially when theeffective concentration of chlorine in the component (A) is adjusted to125 ppm. A part of the components of the composition may remainundissolved in the aqueous solution as used herein.

The aqueous solution comprising hypochlorous acid (A) can be obtained bya conventional method for producing electrolytic oxidation water, forexample by electrolysis of an aqueous solution comprising anelectrolyte, or by acid precipitation of a hypochlorite.

The available concentration of chlorine was determined by an “iodometry”according to JIS K-0101 in this invention.

The preferable concentration of (A) in the aqueous solution to be incontact with microorganisms, or the available chlorine concentration isin the range of 5 ppm to 5% by weight, preferably 5 ppm to 1% by weight,particularly 5 to 5000 ppm, more particularly 5 to 1000 ppm, furtherparticularly 5 to 500 ppm, and most preferably 50 to 200 ppm.

The available chlorine concentration may be also in the range of 1 to5000 ppm, preferably 5 to 2000 ppm.

The components (A), (B) and (C), and the ratio among them are preferablyincluded in the examples in the embodiments to be described hereinafter.One example described in one embodiment may be used as an example in theother embodiment.

Additives other than (A), (B) and (C) described in one embodiment may beused in any embodiments in the present invention. Optional componentsmay be involved in any compositions of the bactericide so long as theydo not impair the properties of the product such as stability.

The present invention provides a bactericide composition having a highbactericidal effect, and being excellent in safety and workability.

The microorganisms as objects of the bactericide composition accordingto the present invention denote common bacteria, fungi, viruses, andspores of fungi and bacteria.

Since the bactericide composition according to the present invention hasa wide bactericidal spectrum and is highly effective for not only fungibut also viruses and spores, it is effective for wide range ofbactericidal applications.

For example, it may be used for sterilization in hospitals, nursinghomes, food processing factories and laundries, as well as sterilizationof walls, floors and windows of a kitchen, and furnishings used therein,and for sterilization of vessels, fixture, containers and others (forexample bottles of beverage).

While the method for allowing the aqueous solution to contact is notparticularly restricted, it include sprinkling, spraying, immersion orfilling, and the subject to be sterilized may be wiped with anappropriate carrier impregnated with the aqueous solution. While thecontact time of the aqueous solution is also not restricted, a contacttime as short as 30 seconds or less, in particular within 10 seconds issufficient for obtaining desired effects. While the temperature duringthe contact is not particularly restricted, a temperature rage of 10 to70° C. is preferable, and a temperature range of 20 to 60° C. isparticularly preferable.

The compositions according to the present invention, in particular thosein the embodiments T and U to be described hereinafter, are favorablefor use in an automatic washer to be used for washing tableware and thelike. The automatic washer as used herein denotes an overall apparatuscapable of continuous or batch wise washing of hard surfaces oftableware such as cups, and delivery trays such as a plastic container,and the size and washing method are not particularly restricted.Sterilization using the automatic washer is more effective when appliedafter removing dirt and other contaminants. For example, it is mostsuitable to spray the composition of the present invention after washingand before final rinsing when the composition is used for a beltconveyer type automatic tableware washer.

Individual component of the composition according to the presentinvention may be independently delivered and stored before use. Eachproduct may be filled in various packages using glass, metal, plasticand paper in the manufacturing process. The ingredient of the productmay be used as it is, or may be used after dilution.

Embodiment R

The embodiment in which the component (B) is an amine oxide and thecomponent (C) is an organic acid or a salt thereof will be describedhereinafter.

The present invention relates to a bactericide composition comprising asalt of hypochlorous acid (A) and an amine oxide (B) in a weight ratio(A)/(B) in the range of 10/1 to 1/10 in addition to the organic acid ora salt thereof.

The present invention also relates to a bactericide comprising theproduct (I) comprising a salt of hypochlorous acid and the product (II)comprising an amine oxide (B), which is prepared as an aqueous solutioncomprising (A) and (B) in a weight ratio (A)/(B) in the range of 10/1 to1/10.

The present invention further relates to a bactericide comprising theproduct (IV) comprising a salt of hypochlorous acid (A) and the product(V) comprising an amine oxide (B) and an organic acid or a salt thereof(C), which is prepared as an aqueous solution comprising (A) and (B) ina weight ratio (A)/(B) in the range of 10/1 to 1/10.

The present invention further relates to a bactericide comprising theproduct (VI) comprising a salt of hypochlorous acid (A) and an amineoxide (B), and a product (VII) comprising an organic acid or a saltthereof (C), which is prepared as an aqueous solution comprising (A) and(B) in a weight ratio (A)/(B) in the range of 10/1 to 1/10.

While a salt of hypochlorous acid (A) to be used in the presentinvention includes sodium hypochlorite, potassium hypochlorite andlithium hypochlorite, sodium hypochlorite is preferable among them.

While an amine oxide (B) to be used in the present invention includesalkyldimethyl amine oxide, those having 8 to 18 alkyl groups arepreferable.

The bactericide composition according to the present invention comprisesa salt of hypochlorous acid (A) and amine oxide (B) in a weight ratio(A)/(B) in the range of 10/1 to 1/10, preferably in the range of 5/1 to1/5, and more preferably in the range of 2/1 to 1/2.

The proportion of (A) is represented by a weight ratio based on theamount of available chlorine.

It is preferable for the bactericide composition according to thepresent invention to comprise further an organic acid or a salt thereof(C) in order to improve bactericidal performance. Examples of theorganic acid or a salt thereof (C) include a saturated dibasic acid suchas malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acidor salts thereof, and an unsaturated dibasic acid such as fumaric acidand maleic acid or salts thereof. The organic acid is preferably asaturated dibasic acid or a salt thereof, more preferably a saturateddibasic acid with a carbon number of 3 to 10 or a salt thereof, andsuccinic acid or a salt thereof is particularly preferable. The weightratio (C)/(A) of organic acid or a salt thereof (C) used and a salt ofhypochlorous acid (A) is preferably in a range of 5/1 to 1/10, morepreferably 2/1 to 1/5, and particularly 1/1 to 1/5.

The bactericide composition according to the present invention maycomprise hydroxides of alkali metals and/or hydroxides of alkaline earthmetals (D). Examples of (D) include sodium hydroxide, potassiumhydroxide and calcium hydroxide, and sodium hydroxide and potassiumhydroxide are preferable among them.

The bactericide composition according to the present invention maycomprise alkali metal salts of inorganic acids and/or alkaline earthmetal salts of inorganic acids (E). Examples of (E) include sodiumsulfate, sodium nitrate, sodium carbonate, sodium hydrogen carbonate,magnesium sulfate, magnesium nitrate, magnesium chloride, magnesiumcarbonate, sodium phosphate, sodium polyphosphate and potassiumphosphate. Sodium sulfate, magnesium sulfate, sodium phosphate, sodiumpolyphosphate and potassium phosphate are preferable among them.

The bactericide composition according to the present invention comprisesan aqueous solution comprising the components (A) and (B) in a specifiedweight ratio. The available chlorine concentration in this aqueoussolution is preferably 5 to 5000 ppm, particularly 50 to 200 ppm. The pHvalue of the aqueous solution (25° C.) is preferably 5 to 12 or 3 to 8,more preferably 5 to 10, further preferably 5 to 8, particularly notless than 5 and less than 7, and more particularly not less than 6 andless than 7. The pH value of the aqueous solution can be adjusted by theorganic acid or the salt thereof (C), and with the inorganic aciddescribed above. The amount of each component in the aqueous solution asthe bactericide composition according to the present invention ispreferably 5 ppm to 12% by weight for the component (A) and 0.5 ppm to35% by weight for the component (B), and the component (C) is preferablyblended in a proportion of 0.5 ppm to 60% by weight. While the aqueoussolution is diluted before use, the diluted aqueous solution comprisesthe component (A) in the range of 5 to 5000 ppm, preferably 10 to 5000ppm and more preferably 50 to 200 ppm, and the component (B) in therange of 0.5 to 50000 ppm, preferably 5 to 2000 ppm and more preferably50 to 200 ppm, and the component (C) in the range of 0.5 to 25000 ppm,preferably 5 to 1000 ppm, more preferably 25 to 500 ppm and particularly25 to 150 ppm. The microorganisms as objects of the bactericidecomposition according to the present invention include common bacteria,molds, viruses, and spores of fungi and bacteria.

The bactericide according to the present invention comprises the product(I) comprising a salt of hypochlorous acid (A) and product (II)comprising an amine oxide (B), and is prepared as an aqueous solutioncomprising (A) and (B) in a weight ratio (A)/(B) in the range of 10/1 to1/10. Optional components may be involved in respective products so longas they do not impair the stability of the products. The bactericide maybe also composed of the product (I) and (II) and furthermore otherproducts.

The organic acid or the salt thereof (C) is preferably blendedindependently from a salt of hypochlorous acid (A), if the former isnecessary. An example of the bactericide comprises the product (IV)comprising a salt of hypochlorous acid (A) and the product (V)comprising an amine oxide (B) and an organic acid or a salt thereof (C),wherein an aqueous solution is prepared by mixing the products (IV) and(V) in a weight ratio (A)/(B) in the range of 10/1 to 1/10 before use.The bactericide is preferably prepared as an aqueous solution comprisingthe components (A) and (C) in a weight ratio (C)/(A) in the range of 5/1to 1/10, preferably in the range of 2/1 to 1/5, more preferably in therange of 1/1 to 1/5. Another example is a bactericide comprisingcomponent (VI) comprising a salt of hypochlorous acid (A) and an amineoxide (B) and the product (VII) comprising an organic acid or a saltthereof (C), wherein the products (VI) and (VII) are mixed as an aqueoussolution comprising (A) and (B) in a weight ratio (A)/(B) in the rangeof 10/1 to 1/10 in use. This bactericide is preferably prepared as anaqueous solution comprising the components (A) and (C) in a weight ratio(C)/(A) in the range of 5/1 to 1/10, particularly in the range of 2/1 to1/5, and more particularly in the range of 1/1 to 1/5. Optionalcomponents may be involved in respective products so long as they do notimpair the stability of each component. The bactericide may comprise theproducts (IV) to (VII) and furthermore other products.

The preferable concentration of each effective ingredient in respectiveproducts is 0.1 to 12% by weight of a salt of hypochlorous acid in theproduct (I), 0.1 to 35% by weight of an amine oxide in the product (II),0.1 to 12% by weight of a salt of hypochlorous acid in the product (IV),a combined amount of 0.2 to 60% by weight of an amine oxide and anorganic acid or a salt thereof in the product (V), a combined amount of0.2 to 47% by weight of a salt of hypochlorous acid and an amine oxidein the product (VI), and 0.1 to 60% by weight in the product (VII).

The bactericide composition according to the present invention can beprepared by combining the products (I) and (II), the products (IV) and(V), or the products (VI) and (VII)with the product (III).

Embodiment S

The embodiment in which the component (A) is hypochlorous acid will bedescribed hereinafter.

The aqueous solution comprising hypochlorous acid (A) can be obtained bya conventional method for producing electrolytic oxidation water knownin the art by, for example, electrolysis of an aqueous solutioncomprising an electrolyte using permeable membranes, or by acidprecipitation of a salt of hypochlorous acid. The concentration ofhypochlorous acid (A) in the bactericide composition according to thepresent invention is preferably 5 ppm to 5% by weight, more preferably 5ppm to 1% by weight, and particularly 5 ppm to 0.5% by weight, as theavailable chlorine concentration, which is determined by JIS K-0101“iodometry”).

The pH range (25° C.) of the bactericide composition according to thepresent invention is 3 to 8, preferably 5 to 8 and more preferably 5 to7. The pH value is adjusted by the pH adjusting agent (C). The pHadjusting agent serves for maintaining the pH value of the compositionaccording to the present invention in the range of 3 to 8 by adding it,and may be selected from compounds to be used for alkaline reagents andbuffer reagents. The pH adjusting agent (C) may have functions otherthan the pH adjusting function.

The pH adjusting agent (C) comprises a hydroxide of an alkaline metal, ahydroxide of an alkaline earth metal, an inorganic acid or a saltthereof, and an organic acid and a salt thereof. Examples of theminclude sodium hydroxide, potassium hydroxide, calcium hydroxide,hydrochloric acid, sodium sulfate, sodium nitrate, sodium chloride,sodium carbonate, potassium hydrogen carbonate, sodium hydrogencarbonate, magnesium sulfate, magnesium nitrate, magnesium chloride,magnesium carbonate, trisodium phosphate, tripotassium phosphate,disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodiumdihydrogen phosphate, potassium dihydrogen phosphate, sodiumpolyphosphate, citric acid, sodium citrate, potassium citrate, potassiumdihydrogen citrate, potassium hydrogen phthalate and succinic acid. Atleast one of the reagent selected from sodium hydroxide, potassiumhydroxide, hydrochloric acid, sodium sulfate, magnesium sulfate, sodiumcarbonate, potassium carbonate, sodium hydrogen carbonate, potassiumhydrogen carbonate, trisodium phosphate, tripotassium phosphate,disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodiumdihydrogen phosphate, potassium dihydrogen phosphate and sodiumpolyphosphate is preferable among them.

The bactericide composition according to the present invention comprisesat least one kind of the surfactant (B). While the surfactant may beselected from the anionic surfactant, cationic surfactant, nonionicsurfactant and amphoteric surfactant, those being stable in the aqueoushypochlorous acid solution are used. The cationic surfactant andamphoteric surfactant are preferable among them, and amine oxides aremost preferable. Alkyldimethyl amine oxides are preferable as the amineoxide, and those having a carbon number of 8 to 18 are preferable. Theratio (A)/(B) of the surfactant (B) and hypochlorous acid (A) asconverted into the available chlorine concentration is preferably 10/1to 1/10 (in weight ratio), more preferably 5/1 to 1/5, and particularly5/1 to 1/2.

The bactericide composition according to the present invention maycomprise the organic acid (C) or a salt thereof as described inEmbodiment R from the view point of improving the bactericidalperformance. The organic acid and a salt thereof may also act as a pHadjusting agent.

The bactericide composition according to the present invention maycomprise thickeners, perfumes and colorants in addition to thecomponents (A), (B) and (C).

While the bactericide composition according to the present invention isused as a diluted aqueous solution, the concentration of the component(A) as converted into the available chlorine concentration in thisdiluted aqueous solution is 5 to 5000 ppm, preferably 5 to 1000 ppm, andparticularly 5 to 500 ppm.

The sterilization method according to the present invention comprisesmaking microorganisms to contact with an aqueous solution comprising thecomponents (A), (B) and (C) at a pH range (25° C.) of 3 to 8, preferably5 to 8 and more preferably 5 to 7 with an available chlorineconcentration of 5 to 5000 ppm, preferably 5 to 1000 ppm andparticularly 5 to 500 ppm. The said microorganisms mean the same asdescribed in the embodiment R.

Embodiment T

The embodiment comprising at least one of the component (A) selectedfrom an alkali metal salt of hypochlorous acid and hypochlorous acid, atleast one of the component (B) selected from the cationic surfactant andamphoteric surfactant, and the pH adjusting agent (C), and having a pHrange of 3 to 8 at 20° C. will be described hereinafter.

An alkali metal salt of hypochlorous acid is preferable as the component(A). While examples of the alkali metal salt of hypochlorous acidinclude sodium hypochlorite, potassium hypochlorite and lithiumhypochlorite, sodium hypochlorite is preferable. The compositionaccording to the present invention has an available chlorineconcentration of preferably 1 to 5000 ppm, more preferably 5 to 1000 ppmand particularly 5 to 500 ppm. It is preferable to use the component (A)so that the available chlorine concentration falls within the rangedescribed above.

While the cationic surfactants as the component (B) include primary,secondary and tertiary amines and quaternary ammonium salts, thequaternary ammonium salts are preferable among them. The quaternaryammonium salts have an alkyl or alkenyl group with a total carbon numberof 8 to 28 as at least one of the four substituents, and the remaininggroups are selected from a benzyl group, an alkyl group with a carbonnumber of 1 to 5, and a hydroxyalkyl group with a carbon number of 1 to5. The alkyl or alkenyl group with the total carbon number of 8 to 28may be substituted with an alkoxy group, an alkenyloxy group, analkanoylamino group, an alkenoylamino group, an alkanoyloxy group or analkenoyloxy group with a carbon number within the range described above.The amphoteric surfactants as the component (B) include an amino acidbased amphoteric surfactant such as a monoaminocarboxylic acid andpolyaminocarboxylic acid, a betaine based amphoteric surfactant such asa N-alkylbetaine, a N-alkylamidobetaine, an N-alkylsulfobetaine, and animidazoline based amphoteric surfactant such as imidazolinium betaine.The N-alkyl betaine is preferable among them, and the N-alkyl betainehaving a carbon number of 12 to 18 is particularly preferable.

The weight ratio (A)/(B) of the composition according to the presentinvention is preferably 10/1 to 1/10, more preferably 5/1 to 1/5, andparticularly 5/1 to 1/2.

Examples of the component (C) include hydroxides of an alkali metal andan alkaline earth metal (D), an inorganic acid and a salt thereof, andan organic acid and a salt thereof. The hydroxides of alkali metals andalkaline earth metals, and the inorganic acids and the salts thereof arethose as described in the embodiment R. Other examples includehydrochloric acid, potassium hydrogen carbonate, potassium hydrogencarbonate, trisodium phosphate, tripotassium phosphate, disodiumhydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogenphosphate and potassium dihydrogen phosphate. The organic acids and thesalts thereof are also those described in the Embodiment R.

The composition according to the present invention preferably has a pHvalue in the range of 3 to 8, more preferably in the range of 5 to 8,and particularly in the range of 5 to 7 at 20° C. The component (C) ispreferably used in an amount so that the pH value falls within thisrange.

The composition according to the present invention is also able to havea stable blend with hypochlorous acid and/or a salt thereof, and ananionic surfactant (F) may be comprised for enhancing the washingeffect. The component (F) include salts of higher fatty acid, sulfuricacid esters of higher alcohol, sulfonic acid esters of higher alcohol,fatty acid sulfate, fatty acid sulfonate, phosphate ester, sulfateesters of fatty acid ester, sulfonate esters of fatty acid esters,sulfate esters of higher alcohol ether, sulfonate esters of higheralcoholic ether, acetate substituted with higher alcohol ethers,condensates of fatty acid and amino acid, alkylol sulfate esters offatty acid amide, alkylsulfonates of fatty acid amide, sulfosuccinicacid ester, alkylbenzene sulfonate, alkylphenol sulfonate,alkylnaphthalene sulfonate, alkylbenzoimidazole sulfonate, amido ethercarboxylic acid or salts thereof, ether carboxylic acid or saltsthereof, N-acyl-N-methylamine or salts thereof, amidoether sulfate orsalts thereof, N-acylglutamic acid or salts thereof,N-amidoethyl-N-hydroxyethyl acetic acid or salts thereof, acyloxyethanesulfonic acid or salts thereof, N-acyl-β-alanine or salts thereof,N-acyl-N-carboxyethyl taurine or salts thereof,N-acyl-N-carboxyethylglycine or salts thereof, and alkyl or alkenylaminocarbonylmethyl sulfuric acid or salts thereof. The amount ofblending of the component (F) is preferably not more than 10 times, morepreferably not more than 5 times, and particularly not more than 2 timesin weight ratio relative to the component (B).

Embodiment U

The embodiment in which the component (B) is a polyhydric alcoholderivative surfactant will be described hereinafter. The component (A)that exhibits the bactericidal effect preferably comprises hypochlorousacid or salts hereof, and alkali metal salts of hypochlorous acid ispreferable among them. While examples of the alkali metal salts ofhypochlorous acid include sodium hypochlorite, potassium hypochloriteand lithium hypochlorite, sodium hypochlorite is preferable.

Examples of the component (B) that improves wettability include glycerinfatty acid esters, polygycerin fatty acid esters, propyleneglycol fattyacid esters, polypropyleneglycol fatty acid esters, sucrose fatty acidesters, sorbitan fatty acid esters and alkylpolyglycoside et al. Thecarbon number at the fatty acid moiety of the various fatty acid estersabove is preferably 6 to 24, and more preferably 6 to 18. The component(B) preferably comprises polygycerin (preferably with a degree ofcondensation of 2 to 50) fatty acid (preferably with a carbon number of6 to 24) esters and alkyl (preferably with a carbon number of 6 to 24)polyglycoside.

The weight ratio (A)/(B) of the components (A) and (B) compositionaccording to the present invention is preferably 1/50 to 50/1, morepreferably 20/1 to 1/20, more preferably 20/1 to 1/5, and particularly20/1 to 1/2.

While the organic acid or the salt thereof as the component (C) is asdescribed in the Embodiment R, examples of them include citric acid,acetic acid, lactic acid, malic acid, tartaric acid and glucuronic acid,succinic acid or a salt thereof is particularly preferable from the viewpoint of the stability of the formulation.

The component (C) is preferably selected from at least one acid and asalt thereof described in The Standard of Food Additives. The component(C) is also preferably selected from at least one acid having carboxylgroups and a salt thereof. The component (A) is distinguished from thecomponent (C).

The pH of the aqueous solution comprising an available chlorineconcentration of 125 ppm at 20° C. is 3 to 8, preferably 5 to 8, morepreferably 5 to 7, and particularly not less than 6 and less than 7. Thecomponent (C) is preferably comprised so that the pH of the solutionfalls within the range described above. The aqueous solution as usedherein include those in which a part of the components remainsundissolved.

The composition according to the present invention is used so that theavailable chlorine concentration is in the range of 1 to 5000 ppm,preferably 5 to 2000 ppm, and particularly 5 to 1000 ppm.

The composition of the present invention may form a stable blending withhypochlorous acid or a salt thereof, and may comprise an anionicsurfactant (F) (referred as the component (F) hereinafter) in order toenhance washing effect. The blended amount of the component (F) ispreferably not more than 10 times, more preferably not more than 5 timesor particularly not more than twice, by weight as much as the component(B).

The bactericide according to the present invention comprises the product(I) comprising the component (A), the product (II) comprising thecomponent (B), and the product (III) comprising the component (C), andis used as an aqueous solution comprising the components (A) (B) and (C)together preferably with an available chlorine concentration of 1 to5000 ppm.

In another embodiment, the bactericide according to the presentinvention comprises the product (IV) comprising the component (A), andthe product (V) comprising the components (B) and (C), and is used as anaqueous solution comprising the components (A), (B) and (C) togetherpreferably with an available chlorine concentration of 1 to 5000 ppm.

Optional components may be comprised in each product in any of theforegoing bactericides, so long as the additive does not impair thestability of the product. The bactericide may comprise the products (I),(II) and (III), or the products (IV) and (V), and furthermore anyproducts other than them.

The products (I) and (IV) preferably comprise the component (A) as aneffective ingredient in a concentration of 0.1 to 12% by weight, theproducts (II) and (V) preferably comprise the component (B) as aneffective ingredient in a concentration of 0.1 to 30% by weight, and theproducts (III) and (V) preferably comprises the pH adjusting agent in aconcentration of 0.1 to 30% by weight. It is preferable for the productto comprise the components (A) and (B) so that the weight ratio (A)/(B)falls within the range of 1/50 to 50/1. The aqueous solution comprisingavailable chlorine concentration of 125 ppm preferably shows a pH valuein the range of 3 to 8 at 20° C.

The bactericide composition according to the present invention can beprepared from the products (I) (II) and (III), or from the products (IV)and (V).

Embodiment V

The present invention is effective as a washing agent composition.

The washing agent is used as an aqueous solution comprising thecomponents (A) and (B) in a weight ratio (A)/(B) of 10/1 to 1/10.

The washing agent according to the present invention comprises theproduct (I) comprising hypochlorous acid (A) and the product (II)comprising amine oxide (B), and is used as an aqueous solutioncomprising the components (A) and (B) in a weight ratio (A)/(B) of 10/1to 1/10. Optional components may be comprised in each product so long asthey do not impair the stability of the product. The washing agent maycomprise the products (I) and (II) as well as any products other thanthem.

When an organic acid or a salt thereof (C) is used, it is preferablyblended independently from hypochlorous acid (A). In particular, thewashing agent comprises the product (IV) comprising hypochlorous acid(A), amine oxide (B) and an organic acid or a salt thereof (C), and isused as an aqueous solution comprising the components (A) and (B) in aweight ratio (A)/(B) in the range of 10/1 to 1/10. The washing agentalso comprises the product (VI) comprising hypochlorous acid (A) andamine oxide (B) and the product (VII) comprising an organic acid or asalt thereof (C), and is used as an aqueous solution comprising thecomponents (A) and (B) in a weight ratio (A)/(B) in the range of 10/1 to1/10. Optional components may be comprised in each product, so long asthey do not impair the stability of the product. The washing agent maycomprise the products (IV) to (VII), and furthermore any products otherthan them.

The concentrations of the effective ingredients in each product are: 0.1to 12% by weight of hypochlorous acid in the product (I); 0.1 to 35% byweight of amine oxide in the product (II); 0.1 to 12% by weight ofhypochlorous acid in the product (IV); a combined proportion of amineoxide and an organic acid or a salt thereof of 0.2 to 60% by weight inthe product (V); a combined proportion of hypochlorous acid and amineoxide of 0.2 to 47% by weight in the product (VII).

The washing agent composition according to the present invention can beprepared from the components (I), (II) and (III), or from the components(IV) and (V), or from the components (VI) and (VII).

The present invention provides a washing agent composition having a highdetergency against oil stain at around a neutral pH, while beingexcellent in safety and workability. It has been generally recognizedthat the detergency is higher at an alkaline pH. However, since thereduction-oxidation potential of hypochlorous acid is higher at theneutral region than at the alkaline region with respect to thecomposition according to the present invention, the detergency is notreduced at the safer neutral region.

Embodiment W

The present invention provides a deodorant composition that exhibit anexcellent deodorant effect against all bad smell generating at a toilet,kitchen, boot cupboard, bathroom, and sheets in theaters and moviehalls.

The present invention relates to a deodorant composition comprising atleast one of the composition (A) selected from hypochlorite andhypochlorous acid, at least one of the composition (B) selected from theamphoteric surfactant and cationic surfactant, and the pH adjustingagent (C).

The present invention also relates to a spray type deodorant filled in avessel having a hand type sprayer, wherein the components (A) and (C)are separately retained in the vessel, the component (B) is storedtogether with at least one of the components (A) and (C), and thecomponents (A), (B) and (C) are mixed together by spraying.

The present invention provides a deodorant composition that can exhibita high deodorant effect by using a small amount of it with a high odorextinguishing rate.

The deodorant composition according to the present invention may be usedin various forms by, for example, impregnating a carrier such as a geland porous material with the composition, by filling a spray bottle(trigger type and dispenser type bottles) with the composition, byforming an aerosol, or by allowing the composition to evaporate by acapillary effect after sucking the composition up into a wick insertedinto the composition that has been filled in a vessel.

Embodiment X

The present invention provides a bactericidal space cleaning compositioncomprising at least one of the component (A) selected from hypochloriteand hypochlorous acid, at least one of the component (B) selected fromthe amphoteric surfactant and cationic surfactant, and the pH adjustingagent (C).

The present invention also provides a method for sterilizing andcleaning the space by discharging the bactericidal space cleaningcomposition according to the present invention as a foam or mist.

An excellent bactericidal and washing effect of the space may beobtained by discharging the bactericidal space cleaning compositionaccording to the present invention as a form or mist. The space as usedherein include spaces in hospital, nursing homes, food manufacturingfactory, kitchen and toilet, and the size and shape of the space is notparticularly restricted.

Embodiment Y

The present invention provides a bactericide composition comprising atleast one of the component (A) selected from hypochlorous acid andalkali metal salts of hypochlorous acid, at least one of the component(B) selected from the cationic surfactant and amphoteric surfactant, atleast one of the component (C) selected from organic acids and saltsthereof, and a rust preventive agent as a component (G).

The component (G) preferably comprises at least one of the acids orsalts selected from phosphoric acid, polyphosphoric acid, sulfonic acidand salts thereof, and the preferable salts include alkali metal saltssuch as sodium salts and potassium salts. The component (G) ispreferably used so that the weight ratio (A)/(G) relative to thecomponents (A) is 10/1 to 1/10, more preferably 10/1 to 1/5, andparticularly 5/1 to 1/5.

EXAMPLES

All the deposited strains of microorganism used in the examples below isobtained from The Institute for Fermentation, OSAKA, IFO located at2-17-85, Juso-Honmachi, Yodogawa-ku, Osaka, Japan, which is described inMicroorganisms 10^(th) List of Culture, 1996. Examples R1 to R6 andComparative Examples R1 to R3

The following experiments were performed using the aqueous solutionsshown in Table R1. The results are listed in Table R1.

The blended composition used in Example R1 was obtained by mixingaqueous solutions of sodium hypochlorite (available chlorineconcentration 60,000 ppm) and amine oxide (effective ingredient 35%),wherein each solution was diluted twice with ion-exchanged water to afinal concentration, and an equal volume each of the diluted solutionswere mixed together. For obtaining the blended compositions used inExamples R2 to R4, a solution was prepared by mixing aqueous solutionsof sodium hypochlorite (available chlorine concentration 60,000 ppm) andamine oxide in a prescribed mixing ratio, the mixed solution was dilutedtwice with ion-exchanged water to a final concentration, and the dilutedsolution was mixed with an equal volume of an aqueous solution ofsuccinic acid prepared by diluting twice with ion exchanged water to afinal concentration. For obtaining the blended compositions used inExamples R5 and R6, an aqueous solution of sodium hypochlorite(available chlorine concentration 60,000 ppm) was diluted twice withion-exchanged water to a final concentration, a mixed aqueous solutionof amine oxide and succinic acid solutions in a prescribed ratio wasdiluted twice with ion exchanged water to a final concentration, and anequal volume each of both diluted solutions were mixed together.

[R1] Sporicide Test

Spores of (1) Bacillus cereus IFO 13494 and (2) Bacillus subtilis ATCC6051 obtained at the heat-treatment by a conventional method to subjectthe spores to a test. Pre-cultured cells on a SCD agar medium (made byNihon Pharmaceutical Ind. Co.) were scratched up with a loop. Thesampled cells were dispersed in 1 ml of sterilized water, heat treatedat 65° C. for 30 minutes followed by washing twice with a centrifuge tosubject the cells to the test.

A 0.1 ml aliquot of the solution of the spores for the test (about 10⁹to 10¹⁰ cells/ml) was sampled. After allowing the sampled cells tocontact 10 ml of an aqueous solution, prepared by diluting each aqueoussolution comprising the components in Table R1 with sterilizedion-exchanged water, for 10 seconds at 25° C., a 50 μl aliquot of thesuspension was sampled and inoculated on a micro-plate (made by CORNINGCo., 96-cell wells) comprising 0.2 ml of a post-culture SCD LP medium(comprising 3.3% of sodium thiosulfate). After incubation at 30° C. for48 hours, growth of the microorganisms on the micro-plate was observedto determine the minimum dilution ratio (the minimum bactericidalavailable chlorine concentration) where no growth of the microorganismswas observed. The available chlorine concentration was determined by“iodometry” according to JIS K-0101.

[R2] Moldicide Test

Molds (fungi, Aspergillus niger IFO6341) were cultured for 7 days at 25°C. using a PDA medium. After homogenizing the cells obtained by a glassbeads method, foreign substances were eliminated by a sheet ofsterilized gauze to obtain a fungus suspension. A 0.1 ml aliquot of thisfungus suspension (about 10⁹ to 10¹⁰ cells/ml) was sampled. Afterallowing the sampled cells to contact 10 ml of an aqueous solution,prepared by diluting an aqueous solution comprising the component inTable R1 with ion-exchanged water at a dilution rate shown in Table R1,for 10 seconds at 25° C., a 0.1 ml aliquot of the test suspension wassampled and inoculated on a post-culture PDA medium (comprising 3.3% ofsodium thiosulfate). Growth of the microorganisms cultured for 7 days at25° C. was observed by the naked eye, and was evaluated as describedabove.

TABLE R1 Example Comparative example R1 R2 R3 R4 R5 R6 R1 R2 R3 Blendedcomponents (weight %) (A) Sodium 1.05 1.05 0.525 1.05 1.05 1.05 1.051.05 1.05 hypochlorite⁽¹⁾ (1) (1) (0.5) (1) (1) (1) (1) (1) (1) (B)Lauryl 2 2 0.25 2 0.05 dimethylamine oxide⁽²⁾ Myristyl 1 1 dimethylamineoxide Polyoxyethylene 1 laurylether sulfate⁽³⁾ (C) Succinic 0.5 0.4 0.50.85 0.85 0.5 acid Hydrochloric acid 0.5 Water Balance Balance BalanceBalance Balance Balance Balance Balance Balance Total 100 100 100 100100 100 100 100 100 pH after diluting to 200 6.5 6.8 6.5 6.8 6.5 6.5 116.8 11 ppm (25° C.) Weight ratio (A)/(B) 1/2 1/2 2/1 1/1 1/2 1/1 20/1 —— Weight ratio (C)/(A) — 1/2 4/5 1/2 4.3/5 4.3/5 — 1/2 — MinimumBacillus 150 125 80 100 60 50 3000 1500 3000 bactericidal cereusavailable Bacillus 300 250 100 200 80 70 5000 2000 5000 chlorinesubtilis concentration Fungus 150 125 50 100 60 50 2000 1500 3000 ppm)⁽¹⁾The figure in the parenthesis denotes the available chlorineconcentration in water before dilution ⁽²⁾Amphitol 20N (made by KaoCorp., effective concentration 35%) ⁽³⁾Mean moles of addition ofethylene oxide: 3 moles, sodium salt

Examples R7 to R10

An aqueous solution comprising the components in Table R2 is dilutedwith ion-exchanged water in a dilution ratio shown in Table R2 toprepare the test aqueous solution comprising (available chlorineconcentration 200 ppm). After sealing the solution in a sample bottle,it was stored in a constant temperature chamber at 40° C. for 2 days. Anaqueous solution of sodium hypochlorite (available chlorineconcentration 60,000 ppm) was diluted twice with ion-exchanged water toa final concentration, and an aqueous solution prepared mixing amineoxide and an organic acid in a prescribed mixing ratio was diluted twicewith ion exchanged water to a final concentration. The test solution wasobtained by mixing an equal volume each of both aqueous solutions.

The sample bottle was taken out of the chamber 2 days after, and theavailable chlorine concentration in the test aqueous solution wasmeasured. The retention ratio (%) of the available chlorineconcentration was determined by the following equation. The results areshown in Table R2.Retention  ratio  (%) = [available  chlorine  concentration  after  2  days^(′)  preservation  at  40^(∘)  C./200] × 100  

TABLE R2 Example R7 R8 R9 R10 Blended components in aqueous solution (%by weight) (A) Sodium hypochlorite 1.05 1.05 1.05 1.05 [figures inparenthesis (1) (1) (1) (1) denotes the available chlorine concentrationof aqueous solution] (B) Lauryl dimethylamine 1 1 1 1 oxide* (C)Succinic acid 0.4 0.85 Fumaric acid 0.3 0.65 Water Balance BalanceBalance Balance Total 100 100 100 100 Weight ratio (A)/(B) 1/1 1/1 1/11/1 Weight ratio (C)/(A) 2/5 3/10 4.3/5 3.3/5 Test Dilution ratio ofaqueous 50 50 50 50 solution solution Effective chlorine 200 200 200 200concentration (ppm) pH 7 7 6.5 6.5 Stability Retention ratio (%) of oneffective chlwrine 80 45 75 40 storage concentration *Amphitol 20N (madeby Kao Corp., effective ingredient 35%)

Examples S1 to S3 and Comparative Examples S1

Aqueous hypochlorous acid solution (pH 2.7 at 25° C., available chlorineconcentration 50 ppm) generated at the anode side of the so-calledelectrolysis oxidation water obtained by a diaphragm membrane method wasused to prepare a bactericide composition by the method described below.The concentration of hypochlorous acid was determined from the availablechlorine concentration measured by “the iodometry” according to JISK-0101.

(1) A bactericide composition is obtained by adjusting the hypochlorousacid solution at pH 5 or pH 11 (comparative example) with an aqueoussolution of 0.1 mole/L sodium hydroxide (Example S1).

(2) A bactericide composition is obtained by adjusting the hypochlorousacid solution at pH 6 with an aqueous solution of 0.1 mole/L sodiumhydroxide, followed by adding lauryl dimethylamine oxide at aconcentration of 25 ppm (Example S2).

(3) A bactericide composition is obtained by adjusting the hypochlorousacid solution at pH 5 with a 0.1 mol/L potassium dihydrogenphosphate/disodium hydrogen phosphate buffer at pH 7 (Example S3).

The following tests were performed using each bactericide composition.The test results are shown in Table S1. Generation of chlorine gas fromeach bactericide composition was suppressed to a low level that arisesno safety problems.

[S1] Sporicide Test

After culturing spores of Bacillus subtilis ATCC 6633 on a SDC agarmedium (made by Nihon Pharmaceutical Industry Co.) for 50 days at 30°C., the cells obtained was washed twice by centrifugation followed by aheat treatment at 65° C. for 30 minutes to prepare a spore suspension(10⁵ cells/ml).

A 50 μl aliquot of the spore suspension was injected in 2 ml of thebactericide composition. After incubation at room temperature for 5minutes, a 50 μl aliquot of the cell contact was sampled, and was seededon a micro-plate (made by CORNING Co., 96-cell wells) filled with 0.2 mlof post-culture SCDLP medium (comprising 3.3% of sodium thiosulfate).After 48 hours' culture at 30° C., growth of the cells was observed bynaked eye to confirm growth of the cells on the micro-plate. The wellswith grown cells were evaluated as ⊚ and without grown cells as ^(x).

[S2] Moldicide Test

A cell suspension (10⁵ cells/ml) was obtained by the same method as inTest R, except that the culture duration time was set at 30 days.

A 50 μl aliquot of this suspension was injected into 2 ml of thebactericide composition and, after allowing the cell to contact thecomposition, a 0.1 ml aliquot of the cell contact solution was sampledand seeded on a post-culture PDA medium (comprising 3.3% of sodiumthiosulfate). After 7 days' culture at 25° C., growth of fungi wasobserved by naked eye to evaluate as described above.

TABLE S1 Comparative Example example S1 S2 S3 S1 Comparison inBactericide composition Hypochlorous acid (as available 50 ppm 50 ppm 50ppm 50 ppm¹⁾ chlorine concentration) Sodium hydroxide pH pH — PHadjustable adjustable Adjustable amount amount amount Potassiumdihydrogen — — pH — Phosphate/disodium hydrogen adjustable phosphatebuffer amount Lauryl dimethylamine oxide — 25 ppm — — Water BalanceBalance Balance Balance pH 5 6 7 11 Bacter- Bacillus subtilis ATCC6633 ⊚⊚ ⊚ x icidal Aspergillus niger IFO6341 ⊚ ⊚ ⊚ x activity ¹⁾Exist as asalt

Examples T1 to T6 and Comparative Examples T1 to T3

The following tests were performed using the compositions comprising thecomponents shown in Table T1, and the results are shown in Table T1. Theavailable chlorine concentration in Table T1 was measured by the“iodometry” according to JIS K-0101.

An aqueous solution was prepared by diluting an aqueous solution,obtained by mixing an aqueous solution of sodium hypochlorite (availablechlorine concentration 60,000 ppm) and the component (B) and/or (C) in aprescribed mixing ratio, twice with ion-exchanged water to a finalconcentration, and another aqueous solution was prepared by diluting anaqueous succinic acid solution twice with ion exchanged water to a finalconcentration. Each composition was obtained by mixing an equal volumeeach of the above solutions.

These compositions were diluted to the available chlorine concentrationsin Table T1 to prepare the aqueous test solutions, which were used forthe bactericidal activity and detergency tests. The results are shown inTable T1.

[T1] Bactericidal Activity

[T1-1] Sporicide Test

Bacillus subtilis ATCC 6633 and Bacillus cereus IFO 13494 as sporeforming bacteria after pre-culture on the SCD agar medium (made by NihonPharmaceutical Industry Co.) were scratched up with a platinum loop. Thesampled bacteria were suspended in 1 ml each of water, and washed twiceby centrifugation after a heat treatment to subject the cells to thetest (cell concentration 10¹⁰ cells/ml in both samples).

A 0.1 ml aliquot of each test spore suspension was seeded in an aqueoussolution (25° C.) prepared by diluting each composition comprising thecomponents in Table T1 with sterilized ion-exchanged water, followed byallowing the test cells to contact the aqueous solution for 3 minutes atroom temperature. A 50 μl aliquot of the cell contact suspension wassampled within 10 seconds, and was seeded on a micro-plate (made byCORNING Co., 96-cell wells) filled with 0.2 ml of a post-culture SCDLPmedium (comprising 3.3% sodium thiosulfate). After 48 hours' culture at30° C., growth of the cells was observed by naked eye to confirm whetherthe cells had grown on the micro-plate, and the minimum dilution ratiowhere no growth of the cells was observed (the minimum bactericidalavailable chlorine concentration) was determined. The available chlorineconcentration was measured by the “iodometry” according to JIS K-1010.

[T1-2] Moldicide Test

Molds (fungi, Aspergillus niger IFO 6341) as a test organism werecultured for 7 days at 25° C. using the PDA medium. After homogenizingthe cells obtained using a glass beads method, foreign substances wereremoved using a sheet of sterilized gauze to obtain a cell suspension(with a concentration about 10⁵ cells/ml). A 0.1 ml aliquot of this cellsuspension was sampled, and seeded in an aqueous solution (25° C.)prepared by diluting each composition in Table T1 with sterilizedion-exchanged water. After allowing the cells to contact eachcomposition for 10 seconds at room temperature, a 0.1 ml aliquot of thesuspension was sampled, which was seeded on a post-culture medium(comprising 3.3% of sodium thiosulfate). After 7 days' culture at 25°C., growth of the cell was observed by naked eye to evaluate asdescribed above.

[T2] Detergency

Models of stain by oil and protein were prepared, and detergency foreach stain was evaluated by a modified Leenerts test method

[T2-1] Detergency for Oil Stains

Twenty grams of an oil stain solution is prepared by dissolving a mixedoil and fat prepared by mixing a tallow and 20 g of soy bean oil in 1:1volume ratio, 0.25 g of monoolein, and 0.1 g of oil red in 60 ml ofchloroform. Each weight of glass plates in a group comprising six platesof clean slide glasses is measured to a digit of 1 mg. The slide glassesare dipped into the oil stain solution at 25±1° C. one by one to a depthof about 55 mm for about 2 seconds, and are taken out after allowingstain to adhere. A mass of stain adhered at the lower end of each slideglass are absorbed using a sheet of cloth such as gaze or filter paper,and the weight of each slide glass on which the oil stain are uniformlyadhered is measured after drying it in the air at 25±1° C. The amount ofthe adhered oil stains is adjusted to be within 0.140±0.010 g per sixplates of the stain model glass pieces. After allowing the stain modelglass plate to dry in the air, it is used for a detergency test within aperiod of not less than 1 hour and not more than 2 hours after thepreparation.

The detergency test was performed as follows. Six groups of the stainmodel glass plates are washed at 25±2° C. for five minutes using aLeenerts modified washing machine, and are rinsed with ion-exchangedwater at 25±2° C. for 30 seconds. The glass plates after completingrinsing are allowed to dry in the air for 24 hours. The detergency isevaluated by measuring the weight of the model stain glass before andafter washing. The detergency (%) is calculated from the weightdifference before and after washing by the following equation:

Detergency(%)=[(weight before washing−weight after washing)/amount ofadhered oil stain]×100

Each detergency for each of the six glass plates is calculated, and thedetergency of the composition was determined from the mean value of thedetergency of the four glass plates after excluding the maximum andminimum detergency from the six glass plates.

[T2-2] Detergency for Protein Stain

A protein stain solution with a total weight of 100 g is prepared bydissolving and diluting 20 g of skim milk powder in ion-exchanged waterat 60° C. A group of clean slide glasses are dipped in the protein stainsolution one by one at 25° C.±1° C. to a depth of 55 mm, and taken outafter allowing protein stain to adhere. A mass of stain adhered at thelower end of the slide glass are absorbed using a cloth such as a sheetof gauze or a sheet of filter paper, and the slide glass is air-dried at25±1° C. after allowing protein stain to uniformly adhere on the glass.This procedure is repeated one more and, after completely removing thestain adhered on one surface of the slide glass, the adhered protein isdenatured by drying at 110° C. in the air for 1 hour to prepare a testpiece. The test piece is subjected to the test within a period of notless than 12 hours and not more than 24 hours after the preparation. Thetest piece is washed at 25° C.±2° C. for 5 minutes using a Leenertsmodified washing machine, and is rinsed with ion-exchanged water for 30seconds at 25° C.±2° C. The test piece is dried at 70° C. for 30 minutesafter rinsing. After drying at 70° C. for 30 minutes after rinsing andstaining the test piece with 1% erythrosine solution, the coloredsurface area (S₁) by photographic judgment, and the detergency (%) iscalculated by the following equation using the initial area (S₀) of theadhered protein stain before washing.

Detergency(%)=[(S ₀ −S ₁)/S ₀]×100

The detergency is calculated for each of the six glass plates, and thedetergency of the composition was determined from a mean value of fourdetergency after excluding the maximum and minimum values of the sixdetergency.

TABLE T1 Example Comparative example T1 T2 T3 T4 T5 T6 T1 T2 T3Bactericidal composition Blended components (A) Sodium hypochlorite⁽¹⁾1.05 1.05 1.05 1.05 1.05 1.05 1.05 1.05 1.05 (1) (1) (1) (1) (1) (1) (1)(1) (1) (B) Quaternary ammonium salt⁽²⁾ 1 1 Benzalkonium chloride⁽³⁾ 1 11 Lauryldimethylamino acetic acid betaine⁽⁴⁾ 1 (C) Succinic acid 0.85 11.75 0.85 0.85 0.85 0.85 (F) Polyoxyethylene laurylether sulfate⁽⁵⁾ 0.2Polyoxyethylene laurylether⁽⁶⁾ 1 Water Balance Balance Balance BalanceBalance Balance Balance Balance Balance Total 100 100 100 100 100 100100 100 100 Bactericidal washing test Test solution Available chlorine500 500 500 500 500 500 500 500 500 concentration (ppm) pH (20° C.) 6.56 5 6.5 6.5 6.5 11 6.5 11 Bactericidal Minimum Bacillus subtilis 150 120120 150 150 200 6000 1500 6000 activity bactericidal Bacillus cereus 120100 100 150 150 200 5000 2000 5000 activity Fungi 100 80 100 120 120 1503000 1000 3000 (ppm) Detergency Detergency of oil stain (%) 46 47 47 4546 43 15 23 25 Detergency of protein stain (%) 42 42 41 40 42 40 12 2120 ⁽¹⁾The figure in the parenthesis denotes the available chlorineconcentration. ⁽²⁾The available chlorine concentration was adjusted tothe values in Table T1 using Quartamin D10P (made by Kao Corp.,effective ingredient 75%). ⁽³⁾The available chlorine concentration wasadjusted to the values in Table T1 using Sanisol C (made by Kao Corp.,effective ingredient 50%). ⁽⁴⁾The available chlorine concentration wasadjusted to the values in Table T1 using Amphitol 24B (made by KaoCorp., effective ingredient 26%). ⁽⁵⁾The available chlorineconcentration was adjusted to the values in Table T1 using Emal 20C(made by Kao Corp., effective ingredient 25%). ⁽⁶⁾The available chlorineconcentration was adjusted to the values in Table T1 using Emulgen 106(made by Kao Corp.).

Example T7 Comparative Example T4

The composition of Comparative Example T4 in Table T2 was obtained usingan aqueous hypochlorous acid solution (pH 2.7 at 25° C., availablechlorine concentration 50 ppm) generated at the anode side of theso-called electrolytic oxidation water obtained by a diaphragm membranemethod, and by adjusting the solution to pH 11 with an aqueous sodiumhydroxide solution at a concentration of 1 mole/L. The composition ofExample T7 was also obtained by adjusting the same aqueous hypochlorousacid solution to pH 5 with an aqueous solution of disodium succinatewith a concentration of 1 mole/L, followed by adding quaternary ammoniumsalt (Quartamin D10P, the same compound as used in Example T1) to be aconcentration of 50 ppm. Bactericidal activity was tested by the samemethod as in Example T1 using the compositions described above. Thebactericidal activity was evaluated as ⊚ or ^(x) in accordance with thepresence or absence of growth of the microorganisms, respectively. Thetest results are listed in Table T2.

TABLE T2 Comparative Example example T7 T4 Blended components (A)Hypochlorous acid 50 ppm 50 ppm (B) Quarternary 50 ppm — ammonium salt(C) Disodium succinate pH adjustable — amount Sodium hydroxide — pHadjustable amount Available chlorine concentration 50 ppm 50 ppm inbactericidal washing solution (ppm) pH (20° C.) 5 11 Bactericidalactivity Bacillus subtilis ⊚ x Bacillus Cereus ⊚ x Fungi ⊚ x

Example U1 to U20 and Comparative Example U1 to U4

The following tests were performed using the diluted aqueous solutions(test aqueous solutions) comprising the compositions shown in Tables U1and U2. The available chlorine concentration in Tables U1 and U2 wasmeasured by the “iodometry” according to JIS K0101.

An equal volume of each of the component (A) and (B) were mixed and, themixture was diluted twice with ion-exchanged water to the finalconcentration. The component (C) was also diluted twice with ionexchanged water to the final concentration. An equal volume of thesediluted solutions were mixed to prepare the test solutions having theavailable chlorine concentration shown in Tables U1 and U2. Thebactericidal activity was tested using these test solutions. The resultsare shown in Tables U1 and U2. The compositions in Examples U1 to U16,U19 and U20, and in Comparative Examples U1 to U4 in the aqueoussolution with an available chlorine concentration of 125 ppm had thesame pH value (20° C.) as that in the test aqueous solutions in TablesU1 and U2 with an available chlorine concentration of 1000 ppm.

[U1-1] Sporicide Test

Bacillus subtilis ATCC 6633 and Bacillus cereus IFO 13494 werepre-cultivated on the SCD agar medium (made by Nihon PharmaceuticalIndustry Co.). Cultured cell were scratched up with a loop, andsuspended in 1 ml of sterilized water. After the heat-treatment at 65°C. for 30 minutes, the cells were washed twice by centrifugation, andwere used for the test (cell concentration 10⁵ cells/ml).

A 0.1 ml aliquot of the test solution was sampled, and was injected into10 ml of an aqueous solution (25° C.) prepared by stepwise dilution ofeach test solution comprising the components in Tables U1 and U2 withsterilized ion-exchanged solution. The cells were allowed to contact thetest solution for 3 minutes at room temperature. A 50 μl of the cellcontacted suspension was sampled within 10 seconds, and was seeded onthe micro-plate that was used in the R1 test and filled with 0.2 ml ofthe same culture medium as used in the post-R1 test. The same cultureand measurements as used in R1 were conducted thereafter.

[U1-2] Moldicide Test

Cell suspension was obtained by the same method as in the R2 test (cellconcentration about 10⁵ cells/ml). A 0.1 ml aliquot of the cellsuspension was sampled, and was injected into an aqueous solution (25°C.) prepared by stepwise dilution of the test aqueous solutioncomprising the components in Table U1 and U2 with sterilized water.After allowing the cells to contact the test aqueous solution for 10seconds, a 0.1 ml aliquot of this suspension was sampled. Cell growthwas observed on the same post-culture PDA medium as used in the R2 test,and was evaluated as in the R2 test.

TABLE U1 Example U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 U12 Bactericidecomposition Blended components (weight %) (A) Sodium hypochlorite 2.11.05 2.1 1.05 1.05 2.1 1.05 2.1 1.05 1.05 2.1 1.05 Hypochlorous acid (B)Glycerin fatty acid ester⁽¹⁾ 1 1 Polyglycerin fatty acid ester⁽²⁾ 1 1 2Propyleneglycol fatty acid ester⁽³⁾ 1 1 Sucrose fatty acid ester⁽⁴⁾ 1 12 Sorbitan fatty acid ester⁽⁵⁾ 1 1 Alkyl polyglycoside⁽⁶⁾ (C) Fumaricacid 1.5 1 2 1 Succinic acid 2 1 1 2 1 1 Disodium succinic acid Citricacid 2 1 Phosphoric acid Bactericidal test Test Available chlorine 10001000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 solutionconcentration (ppm) pH (20° C.) 6.1 5.2 6.2 6.2 6.2 5.5 5.5 6.2 6.2 6.25.2 5.2 Bactericidal Minimum Bacillus cereus 250 250 62.5 62.5 62.5 250250 125 125 125 125 125 activity bactericidal Bacillus subtilis 125 12531.3 62.5 62.5 125 125 62.5 6.2 6.2 6.2 6.2 concen- Fungi 250 125 62.562.5 31.3 250 125 62.5 62.5 31.3 62.5 62.5 tration (ppm)

TABLE U2 Example Comparative example U13 U14 U15 U16 U17 U18 U19 U20 U1U2 U3 U4 Bactericide composition Blended components (weight %) (A)Sodium hypochlorite 1.05 2.1 1.05 1.05 1.05 1.05 1.05 1.05 1.05Hypochlorous acid 2.1 2.1 (B) Glycerin fatty acid ester⁽¹⁾ Polyglycerinfatty acid ester⁽²⁾ 1 1 1 1 Propyleneglycol fatty acid ester⁽³⁾ Sucrosefatty acid este⁽⁴⁾ Sorbitan fatty acid ester⁽⁵⁾ 2 Alkyl polyglycoside⁽⁶⁾1 1 2 1 1 1 (C) Fumaric acid 1 Succinic acid 2 1 1 1 1 25 DisodiumSuccininc acid pH pH adjusta- adjusta- ble ble amount amount Citric acidPhosphoric acid 1 1 Bactericidal test Test Available chlorine 1000 10001000 1000 125 125 1000 1000 1000 1000 1000 1000 solution concentration(ppm) pH (20° C.) 5.2 6.2 6.2 6.2 6.0 6.0 6.0 6.0 6.2 3.5 9.0 8.5Bactericidal activity Minimum Bacillus cereus 125 31.3 62.5 62.5 62.531.3 125 62.5 1000 over over over bacteri- 1000 1000 1000 cidal Bacillussubtilis 625 31.3 31.3 31.3 31.3 31.3 62.5 62.5 500 over over overconcentra- 1000 1000 1000 tion (ppm) Fungi 31.3 31.3 31.3 31.3 62.5 31.3125 62.5 over over over over 1000 1000 1000 1000 ⁽¹⁾Excel VS-95 (made byKao Corp.) ⁽²⁾MCA-750 (made by Sakamoto Pharmaceutical Industry Co.)⁽³⁾Homotex PS-200 (made by Kao Corp.) ⁽⁴⁾LWA1570 (made by MitsubishiFoods Co.) ⁽⁵⁾Emasol O-10 (made by Kao Corp.) ⁽⁶⁾Mydol 12 (made by KaoCorp.)

The phrase “pH adjusting amount” of the component (C) in Examples U17and U18 means an amount by which the pH value of the test aqueoussolution becomes that in Table U1.

What is claimed is:
 1. A liquid bactericide composition comprising:hypochlorous acid or an alkali metal salt thereof (A), a surfactant (B),and a pH adjusting agent (C), wherein said composition is an aqueoussolution having a pH value (25° C.) of 5 to 7 and wherein the weightratio of (A)/(B) in the aqueous solution is in the range of 2/1 to 1/2,and the weight ration of (C)/(A) in the aqueous solution is in the rangeof 2/1 to 1/5, and the available chlorine concentration of (A) in theaqueous solution if from 25 to 500 ppm.
 2. The bactericide compositionaccording to claim 1, wherein the weight ratio (C)/(A) between the pHadjusting agent (C) and hypochlorous acid and/or a salt thereof (A) is1/1 to 1/5.
 3. The bactericide composition according to claim 1, whereinthe surfactant (B) is at least one selected from the group consisting ofamphoteric surfactants, cationic surfactants and nonionic surfactants.4. The bactericide composition according to claim 1, wherein thesurfactant (B) is an amine oxide.
 5. The bactericide compositionaccording to claim 1, wherein the surfactant (B) is a polyhydric alcoholderivative surfactant.
 6. The bactericide composition according to claim1, wherein the pH adjusting agent (C) is an organic acid or a saltthereof.
 7. The bactericide composition according to claim 6, whereinthe organic salt or a salt thereof is a saturated dibasic acid or a saltthereof.
 8. A bactericide comprising the liquid bactericide compositionof claim 1, wherein components (A), (B) and (C) are individualcomponents and then mixed together to obtain said liquid bactericidetherefore composition.
 9. A bactericide comprising liquid bactericidecomposition of claim 1, wherein component (A) is an individual componentthat is mixed with components (B) and (C) to obtain said liquidbactericide therefore composition.
 10. A bactericide comprising liquidbactericide composition of claim 1, wherein component (C) is anindividual component that is mixed with components (A) and (B) to obtainsaid liquid bactericide therefore composition.
 11. The bactericideaccording to any one of claims 8 to 10, wherein the pH adjusting agent(C) is an organic acid or a salt thereof.
 12. The bactericide accordingto claim 11, wherein the organic acid or a salt thereof is a dibasicorganic acid or a salt thereof.
 13. The bactericide according to claim8, wherein the surfactant (B) is at least one selected from the groupconsisting of amphoteric surfactants, cationic surfactants and nonionicsurfactants.
 14. The bactericide according to claim 8, wherein thesurfactant (B) is an amine oxide.
 15. The bactericide according to claim8, wherein the surfactant is a polyhydric alcohol derivative surfactant.16. The bactericide composition according to claim 1, wherein saidalkali metal salt of hypochlorous acid is selected from the groupconsisting of sodium hypochlorite, potassium hypochlorite and lithiumhypochlorite.